Quaternary salts of methacrylic or acrylic esters and cationic quaternay polyelectrolytes and ion exchange resins thereof

ABSTRACT

The invention relates to quaternary cationic monomers and polymers and copolymers prepared thereof, based upon salts of methacrylic or acrylic esters of the general formula I ##STR1## where R 1  is H or CH 3   
      r.sup. 2  is CH.sub. 3 , C.sub. 6 H.sub. 5  or p-CH.sub. 3 C.sub. 6 H.sub. 4 
     n is 1 or 2, and 
     Y +  is --N + (CH 3 ) 3 , --N + (CH 3 ) 2  CH 2  CH 2  OH, ##STR2## where R 3  is H, CH 3 , CONH 2 , CHO, COCH 3  and 
     R 4  is H or CH 2  CH 2  OH. 
     The invention further relates to some methods for preparation of monomers, polymers and copolymers of the aforegiven salts. The polymers and copolymers exhibit the properties of polyelectrolytes and ion exchange resins.

STATEMENT OF THE OBJECT OF THE INVENTION

Monomers of the methacrylate type are often used for the preparation ofcationic polyelectrolytes. They can be obtained essentially in two ways.Either by alkylation of tertiary aminoalkyl methacrylates by analkylation agent or by alkylation of tertiary amines by an alkylatingmethacrylate.

Among the analogous compounds, methacrylic ester of2-hydroxyethyltrimethylammonium methylsulfate, ##STR3## which isproduced by methylation of 2-dimethylaminoethyl methacrylate (Brit. Pat.No. 784,051 and U.S. Pat. Nos. 2,677,679 and 2,824,861), obtained a widetechnological use. Further, the preparation of methacrylic ester of1-(2-hydroxyethyl)pyridinium chloride by the reaction of 2-chloroethylmethacrylate with pyridine was described (Brit. Pat. No. 784,051).

According to the invention, monomeric quaternary salts of methacrylic oracrylic esters of the general formula II ##STR4## are prepared by thereaction of sulfoester of the general formula III ##STR5## with thecorresponding tertiary amine. The meaning of substituents R¹,R² and Y⁺and of the symbol n in the formulas II and III are the same as in theaforementioned formula I.

This reaction can be advantageously carried out in the presence ofpolymerization inhibitors, without solvent or in an inert solvent atambient or elevated temperature. The product may be purified, forinstance, by dissolving in water and extraction of unreacted componentsby a suitable solvent.

An advantage of the presented method is employment of the largealkylation power of sulfoester group. The reaction proceeds under mildconditions and reaches high yield. It is possible to prepare productsderived from less reactive tertiary bases, which require in thepreparation from chloro derivatives long reaction periods and hightemperature, i.e. the conditions when the thermically inducedpolymerization interferes even in the presence of an inhibitor. Anotheradvantage is that sulfoester III can be prepared from a hydroxyderivative (e.g. 2-hydroxyethyl methacrylate) which contains variousamounts of a divinylic component (ethylene dimethacrylate). The lattercompound remains unchanged in the reaction mixture and is advantageouslyremoved together with an inhibitor and any unreacted starting materialby extraction of the aqueous solution. This extracted solution can bethen advantageously directly used for polymerization.

The employment of much more reactive sulfoesters of hydroxyalkylmethacrylates enables to prepare quaternary methacrylates derived fromlow reactive amines, namely heterocyclic bases, as well as to carry outthe reaction at milder conditions, especially at lower temperatures andfor shorter periods of time, even with low reactive amines.Consequently, the yields are enhanced and the problems with inhibitionof the reaction mixture are reduced. The polymerization itself has anadvantage that, unlike the chloride anion, the sulfonate anion does notinterfere the polymerization by transfer. The monomers prepared can becopolymerized with various known vinylic and divinylic comonomers,especially with those able to undergo a free-radical polymerization.

The invention permits to prepare, if needed, a broad choice ofderivatives of numerous aliphatic or heterocyclic bases, both monomersand their polymers or copolymers. High-molecular-weight polymers orcopolymers can be used, above all, as flocculants and coagulants inwater treatment, where they gave very good results. The polymers andcopolymers according to this invention can be further used in the wayknow for other cationic polyelectrolytes, for instance, as additives inpaper production, for improving the dyeability of fibers, in productionof selective permeable membranes, etc.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

The invention relates to quaternary salts, based upon methacrylic oracrylic esters, of the general formula II, ##STR6## where R¹ is H or CH₃

R² is CH₃, C₆ H₅ or p-CH₃ C₆ H₄

n is 1 or 2 and

Y⁺ is ##STR7## where R³ is H, CH₃, CONH₂, CHO, COCH₃ and

R⁴ is H or CH₂ CH₂ OH.

The method for preparation of cationic quaternary salts, based uponmethacrylic or acrylic esters, of the general formula II ##STR8## whereR¹ is H or CH₃

R² is CH₃, C₆ H₅ or p-CH₃ C₆ H₄

n is 1 or 2 and

Y⁺ is either aliphatic, --N⁺(CH₃)₃ or --N⁺(CH₃)₂ CH₂ CH₂ OH, orheterocyclic ##STR9## where R³ is H, CH₃, CONH₂, CHO, COCH₃ and

R⁴ is H or CH₂ CH₂ OH,

consists in the reaction of sulfoesters of the general formula III##STR10## where R¹, R², and n have the same meaning as in the formulaII, with the corresponding tertiary amine.

The reaction can be carried out in the presence of a polymerizationinhibitor, without solvent or in an inert solvent, at the ambient orelevated temperature. The product can be purified, for example, bydissolving in water and subsequent extraction of unreacted componentswith a suitable solvent. The polymerization can be carried out in block,solution or emulsion in the presence of known free-radical initiatorsand also in the presence of further comonomers able to undergo thefree-radical polymerization, e.g. methyl methacrylate, acrylonitrile,acrylamide, vinylpyridine, etc. Ion exchange resins are obtained whendivinylic comonomers have been used, e.g. ethylene dimethacrylate,methylene-bis-acrylamide, etc. The aqueous solution of the monomer afterextraction of an inhibitor may be directly used for the solution oremulsion polymerization, without isolation of the monomer.

An advantage of the invented method is employment of a large alkylationpower of the sulfoester group. The reactions are carried out under mildconditions and reach high yields. It is also possible to prepareproducts derived from less reactive tertiary amines, which require inthe preparation from chloro derivatives long reaction periods and hightemperatures, i.e. the conditions when the thermally inducedpolymerization interferes even in the presence of an inhibitor. Anotheradvantage is that sulfoester III can be prepared from a hydroxyderivative (e.g. 2-hydroxyethyl methacrylate), which contains variousamounts of a divinylic component (ethylene dimethacrylate). The lattercompound remains unchanged in the reaction mixture and is advantageouslyremoved together with an inhibitor and other respective unreactedreaction components by extraction of the aqueous solution. This aqueoussolution can be then advantageously directly used for polymerization.

The polymerization according to the invented method has the furtheradvantage consisting in the fact that, unlike the chloride anion, thesulfonate anion does not interfere the polymerization by transfer.

This invention is further illustrated, but by no means limited, in thefollowing examples.

EXAMPLE 1

Methacrylic ester of 2-hydroxyethyltrimethylammonium benzenesulfonate

2-(Benzenesulfonyloxy)ethyl methacrylate (20 parts) and 0.6 parts ofnitrobenzene in 6.2 parts of trimethylamine and 45 parts of acetone wasallowed to stand at 25° C for 16 hours and then heated to 40° C for 5hours. Acetone and the excess of trimethylamine were removed in vacuum.The residue, crystalline in part, was dissolved in 125 parts of waterand the solution was continuously extracted with ether for 2 hrs. Theresidual ether was removed from the aqueous phase in vacuum. Thesolution contained 19.7 parts of the monomer (80.9%) according to thetitrimetric determination of anion (argentometric determination ofchloride after exchange with an ion exchange resin).

EXAMPLE 2

Methacrylic ester of 2-(2-hydroxyethoxy)ethyltrimethylammoniumbenzenesulfonate

2-[2-(Benzenesulfonyloxy)ethoxy] ethyl methacrylate (12.6 parts), 0.2parts of nitrobenzene and a solution of 3.5 parts of trimethylamine in60 parts of acetone were allowed to stand at the ambient temperature for40 hours. The reaction mixture was worked out similarly as in EXAMPLE 1,and the aqueous solution was obtained which contained 13.7 parts of themonomer (87% of theoretical yield).

EXAMPLE 3

Methacrylic ester of 1-(2-hydroxyethyl)pyridinium benzenesulfonate

A mixture of 50 parts of 2-(benzenesulfonyloxy)ethyl methacrylate, 16.1parts of pyridine and 1 part of octylpyrocatechol was stirred and heatedto 90° C for 105 min. The reaction product was dissolved in 250 parts ofwater and the solution was continuously extracted with ether for 2 hrs;the residues of ether were removed in vacuum. The resulting solutioncontained 60.6 parts of the monomer (94% of theoretical yield);determined as in EXAMPLE I.

EXAMPLE 4

Methacrylic ester of 1-(2-hydroxyethyl)pyridinium p-toluenesulfonate

A mixture of 20 parts of 2-(p-toluenesulfonyloxy)ethyl methacrylate, 6.1parts of pyridine and 0.4 parts of octylpyrocatechol was stirred andheated to 90° C for 90 min. The reaction mixture was worked outanalogously as in EXAMPLE 3 and the solution was obtained containing24.5 parts of the monomer (95.6% of theoretical yield).

EXAMPLE 5

Methacrylic ester of 1-[2-(2-hydroxyethoxy)ethyl] pyridiniumbenzenesulfonate

A mixture of 20 parts of 2-[2-(benzenesulfonyloxy)ethoxy]-ethylmethacrylate, 6.9 parts of pyridine and 0.5 parts of octylpyrocatecholwas stirred and heated to 90° C for 105 min. The reaction mixture wasworked out analogously as in EXAMPLE 3 and the solution was obtainedcontaining 30.2 parts of the monomer (96.6% of theoretical yield).

EXAMPLE 6

Methacrylic ester of 1-[2-(2-hydroxyethoxy)ethyl] pyridiniump-toluenesulfonate

A mixture of 20 parts of 2-[2-(p-toluenesulfonyloxy)ethoxy]-ethylmethacrylate, 5.3 parts of pyridine and 0.5 parts of octylpyrocatecholwas stirred and heated to 90° C for 2 hrs. After the reaction mixturewas worked out analogously as in EXAMPLE 3, the solution was obtainedcontaining 24 parts of the monomer (97% of theoretical yield).

EXAMPLE 7

Methacrylic monoester of di(2-hydroxyethyl)dimethylammoniumbenzenesulfonate

A mixture of 20 parts of 2-(benzenesulfonyloxy)ethyl methacrylate, 6.58parts of dimethylaminoethanol and 3 parts of nitrobenzene was heated to90° C for 60 min. After the reaction mixture was worked out analogouslyas in EXAMPLE 3, the solution was obtained containing 25.4 parts of themonomer (95.4% of theoretical yield).

EXAMPLE 8

Methacrylic ester of 1-(2-hydroxyethyl)-3-carbamidopyridiniumbenzenesulfonate

A mixture of 12.2 parts of 2-(benzenesulfonyloxy)ethyl methacrylate, 5parts of nicotinamide and 2.43 parts of nitrobenzene was stirred andheated to 90° C for 2 hrs. The reaction mixture gradually turned solid;the raw product melted 134° - 136° C and after crystallization fromethanol 137° - 138° C. The reaction mixture was worked out analogouslyas in EXAMPLE 3 and the solution was obtained containing 11 parts of themonomer (68.9% of theoretical yield).

EXAMPLE 9

Methacrylic ester of 1-[2-(2-hydroxyethoxy)ethyl]-3-carbamidopyridiniumbenzenesulfonate

A mixture of 14.2 parts of 2-[2-(2-benzenesulfonyloxy)ethoxy]-ethylmethacrylate, 5 parts of nicotinamide and 2.8 parts of nitrobenzene wasstirred and heated to 90° C for 2 hours. The liquid product solidifiedby cooling into a crystalline mass melting 107° - 110° C; afterrecrystallization from ethanol the product melted at 116° C. Thereaction mixture was worked out analogously as in EXAMPLE 3 and thesolution was obtained containing 16.6 parts of the monomer (93.1% oftheoretical yield).

EXAMPLE 10

Methacrylic ester of 3-[2-(2-hydroxyethoxy)ethyl]-4-methylthiazoliumbenzenesulfonate

A mixture of 18 parts of 2-[2-(benzenesulfonyloxy)ethoxy]-ethylmethacrylate, 5 parts of 4-methylthiazole and 3.6 parts of nitrobenzenewas heated to 90° C for 150 min. The reaction mixture was worked outanalogously as in EXAMPLE 3 and the solution was obtained containing12.1 parts of the monomer (58.7% of theoretical yield).

EXAMPLE 11

Methacrylic ester of3-[2-(2-hydroxyethoxy)ethyl]-4-methyl-5-(2-hydroxyethyl)thiazoliumbenzenesulfonate

A mixture of 7.28 parts of 2-[2-(benzenesulfonyloxy)ethoxy]-ethylmethacrylate, 3 parts of 4-methyl-5-(2-hydroxyethyl)-thiazole and 1.1parts of nitrobenzene was heated to 90° C for 150 min. The reactionmixture was worked out analogously as in EXAMPLE 3 and the solution wasobtained containing 6.33 parts of the monomer (59.7%).

EXAMPLE 12

Methacrylic ester of 2-hydroxyethyltrimethylammonium toluenesulfonate

2-(Toluenesulfonyloxy)ethyl methacrylate (50 parts) and 0.85 parts ofnitrobenzene in a solution of 14.2 parts of trimethylamine and 90 partsof acetone were allowed to stand at 25° C for 15 hrs and then heated to40° C for 5 hrs. The product was freed from acetone and excessivetrimethylamine in vacuum. A crystalline residue (m.p. 124° - 5° C; fromacetone) was dissolved in 125 parts of water and continuously extractedby ether for 2 hrs. The aqueous solution was freed from ether residuesin vacuum and contained 42.3 parts of the monomer, according to atitrimetric determination of the anion.

EXAMPLE 13

Acrylic ester of 2-hydroxyethyltrimethylammonium benzenesulfonate

2-(Benzenesulfonyloxy)ethyl acrylate (10 parts) and 0.32 parts ofnitrobenzene in a solution of 3.2 parts of trimethylamine and 21 partsof tetrahydrofuran were allowed to stand at 25° C for 18 hrs. Theproduct gradually precipitated from the solution. The excessivetrimethylamine and tetrahydrofuran were evaporated in vacuum. Thecrystalline residue was dissolved in 68 parts of water and continuouslyextracted with ether for 2 hrs. The resulting aqueous solution contained9.75 parts of the monomer, according to a titrimetric determination.

EXAMPLE 14

Polymerization of methacrylic ester of 1-(2-hydroxy)ethyl-pyridiniumbenzenesulfonate

A solution of 25.8 parts of the monomer in 100 parts of water wasstirred and heated to 60° C in an inert atmosphere with 0.036 parts ofazo-bis(methyl isobutyrate) for 4 hrs. The polymer can be isolated byprecipitation into excess of acetone.

Conversion of the monomer 90%,[η] = 1.32 (in 0.5 N KCl ).

EXAMPLE 15

Polymerization of methacrylic ester of 1-[2-(2-hydroxyethoxy)-ethyl]pyridinium benzenesulfonate

A solution of 24.2 parts of the monomer in 85 parts of water was stirredand heated to 60° C in an inert atmosphere with 0.015 parts ofazo-bis(methylisobutyrate) for 6 hrs. By precipitation into acetone 21.3parts of the polymer was obtained, [η] = 2.5 (in 0.5 N KCl).

EXAMPLE 16

Poymerization of methacrylic ester of 1-(2-hydroxyethyl)pyridiniump-toluenesulfonate

A solution of 10 parts of the monomer in 36 parts of water was heated to60° C with 0.027 parts of azo-bis(methyl isobutyrate) under an inertatmosphere for 6 hrs. After cooling the solution down to the ambienttemperature, 9 parts of the polymer precipitated, [η] = 0.61 (in 0.5 NKCl).

EXAMPLE 17

Polymerization of methacrylic ester of3-[2-(2-hydroxyethoxy)-ethyl]-4-methylthiazolium benzenesulfonate

A solution of 5 parts of the monomer in 27 parts of water was heated to50° C under an inert atmosphere with 0.006 parts of azo-bis(methylisobutyrate) for 10 hours. By precipitation into acetone 4.41 parts ofthe polymer was obtained, [η] = 1.58 (in 0.5 N KCl).

EXAMPLE 18

Polymerization of methacrylic ester of 2-(2-hydroxyethoxy)ethyltrimethylammonium benzenesulfonate

A solution of 6.85 parts of the monomer in 40 parts of water was heatedto 60° C under an inert atmosphere with 0.025 parts of potassiumpersulfate for 4 hrs. The viscous solution was precipitated into anexcess of acetone and 5.60 parts of the polymer was obtained, [η] = 1.05(in 0.5 N KCl).

EXAMPLE 19

Copolymerization of methyl methacrylate in emulsion

A mixture of 25 parts of methyl methacrylate, 4.27 parts of methacrylicester of 1-(2-hydroxyethyl)pridinium benzenesulfonate, 25 parts of waterand 0.05 parts of potassium persulfate was agitated and heated to 60° Cunder an inert atmosphere for 6 hrs. The thick reaction mixture wasstirred with 50 parts of water, centrifugated and the residue was washedthreetimes with 50 parts of water and dried; 22.5 parts of the copolymerwas obtained which contained 0.35% N.

EXAMPLE 20

Polymerization of methacrylic ester of 2-hydroxyethyltrimethylammoniumbenzenesulfonate

A solution of 10 parts of the monomer in 51 parts of water was heated to60° C under an inert atmosphere with 0.035 parts of azo-bis(methylisobutyrate) for 8 hrs. The polymer (8.7 parts) was obtained byprecipitation into 450 parts of acetone; [η] = 1.6 (in 0.5 N KCl).

EXAMPLE 21

Polymerization of methacrylic ester of3-(2-hydroxyethyl)-4-methylthiazolium benzenesulfonate

A solution of 5 parts of the monomer in 21.4 parts of water was heatedto 60° C with 0.011 parts of azo-bis(methyl isobutyrate) under an inertatmosphere for 6 hrs. The polymer (4.45 parts) was obtained byprecipitation into 200 parts of acetone; [η] = 0.86 (in 0.5 N KCl).

EXAMPLE 22

Polymerization of methacrylic ester of1-(2-hydroxyethyl)-3-carbamidopyridinium benzenesulfonate

A solution of 6 parts of the monomer in 40 parts of water and 0.012parts of azo-bis(methyl isobutyrate) was heated to 60° C in an inertatmosphere for 20 hrs. The polymer (2.54 parts) was obtained byprecipitation into 320 parts of acetone.

EXAMLE 23

Polymerization of acrylic ester of 2-hydroxyethyltrimethylammoniumbenzenesufonate

A solution of 5 parts of the monomer in 10.7 parts of water and 0.017parts of azo-bis(methyl isobutyrate) was heated to 55° C under an inertatmosphere for 6 hrs. The polymer (4.0 parts) was obtained byprecipitation into 124 parts of acetone; [η] = 0.36 (in 0.5 N KCl).

EXAMPLE 24

Polymerization of methacrylic ester of 2-hydroxyethyltrimethylammoniump-toluenesulfonate

A solution of 5 parts of the monomer in 26.2 parts of water and 0.01part of azo-bis(methyl isobutyrate) was heated to 60° C for 3 hrs. Thepolymer (4.4 parts was obtained by precipitation into 242 parts ofacetone; [η] = 1.18 (in 0.5 N KCl).

EXAMPLE 25

Copolymerization of methacrylic ester of2-(hydroxyethyl)trimethylammonium p-toluenesulfonate with acrylamide

A solution of 2.68 parts of methacrylic ester of2-(hydroxyethyl)-trimethylammonium toluenesulfonate and 5.0 parts ofacrylamide 32.7 parts of water with 0.027 parts of (NH₄)₂ S₂ O₈ and0.021 parts of Na₂ S₂ O₄ was heated to 45° C under an inert atmospherefor 3 hrs. The polymer (7.5 parts) containing 3.16% S was obtained byprecipitation into 310 parts of acetone; [η] = 1.12 (in 0.5 N KCl).

We claim:
 1. Homopolymers comprising the monomer of the general formulaI ##STR11## wherein R¹ is H or CH₃ R² is CH₃, C₆ H₅ or p-CH₃ C₆ H₄ n is1 or 2 and Y⁺ is ##STR12## where R³ is H, CH₃, CONH₂, CHO, COCH₃ and R⁴is H or CH₂ CH₂ OH.
 2. A polymer according to claim 1, wherein R¹ isCH₃, R² is C₆ H₅, n is 1 or 2 and Y⁺ is ##STR13##
 3. A polymer accordingto claim 1, wherein R¹ is CH₃, R² is p--CH₃ C₆ H₄, n is 1, and Y⁺ is##STR14##
 4. A polymer according to claim 1, wherein R¹ is CH₃, R² is C₆H₅, n is 1, and Y⁺ is ##STR15##
 5. A polymer according to claim 1,wherein R¹ is CH₃, R² is C₆ H₅,n is 2, and Y⁺ is ##STR16##
 6. A polymeraccording to claim 1, wherein R¹ is CH₃, R² is C₆ H₅, n is 1, and Y⁺ is##STR17## wherein R³ is H. CH₃, CONH₂, CHO, COCH₃.
 7. Bipolymers of (1)a monomer of the general formula I ##STR18## wherein R¹ is H or CH₃ R²is CH₃, C₆ H₅ or p-CH₃ C₆ H₄ n is 1 or 2 and Y⁺ is ##STR19## where R³ isH, CH₃, CONH₂, CHO, COCH₃ and R⁴ is H or CH₂ CH₂ OHand (2) a monovinylicmonomer selected from the group consisting of methyl methacrylate,acrylonitrile, acrylamide, and vinylpyridine or a divinylic monomerselected from the group consisting of ethylene dimethacrylate andmethylene-bis-acrylamide.
 8. Copolymers according to claim 7, whereinthe monovinylic monomer is methyl methacrylate.
 9. Copolymers accordingto claim 7, wherein the monovinylic monomer is acrylonitrile. 10.Copolymers according to claim 27, wherein the monovinylic monomer isacrylamide.
 11. Copolymers according to claim 7, wherein the monovinylicmonomer is vinylpyridine.
 12. Copolymers according to claim 7, whereinthe divinylic monomer is ethylene dimethacrylate.
 13. Copolymersaccording to claim 7, wherein the divinylic monomer ismethylene-bis-acrylamide.